I-soanha



United States Patent C) 3,10,840 FORMAZANE DYESTUFFS CGNTAlNH IG HEAVYMETAL Fabio Bena and Guido Schetty, Basel, Switzerland, as-

signors to .l. R. Geigy A.-G., Basel, Switzerland No Drawing. Filed Dec.23, 1960, Ser. No. 77,321 Clm'ms priority, application Switzerland Dec.24, 1959 6 (Ilaims. (Cl. 260-149} The present invention concerns new,heavy metal-containing dyestuffs of the formazane series, processes forthe production thereof, also the use of these dyestuffs for the dyeingand printing of organic materials, in particular textile material, and,as industrial product, the material fast dyed with these dyestufis.

It has been found that heavy metal-containing formazaue compounds inwhich the heavy metal is co-ordinated at at least one sulphonylamidogroup of the formula in which X is an organic radicfl, are stabledyestuffs which are well suited for dyeing purposes.

The dyestuiis according to the invention are the heavy metal complexesof formazanecompounds of the general In this formula:

The new formazane compounds used according to the invention of thegeneral Formula I are obtained by methods known per se using startingmaterials which contain a group of the general Formula II wherein X hasthe meaning given above and Z represents hydrogen or a substituent whichcan be exchanged therefor.

For example, an aryl diazonium compound containing a sulphonylamidogroup of the Formula II in o-position to the diazo group, in which thesubstituent Z is a radical which can be split off, preferably an acidradical and in particular an X-SO radical, is used; principally a diazocompound of the benzene series is used.

This aryl diazonium compound is coupled, for example,

attests Patented Nov. 5, 1953 with an arylazomethylene or anarylazomethine compound coupling at the methylene or methine grouprespectively, and at a suitable stage in the formation of the formazane,the substituent Z is replaced by hydrogen, i.e. in the preferred case bysaponification of a disulphonylamido group to the monosulphony'lamidogroup XSO --NH-. The second component, i.e. the arylazomethylene orarylazomethine compound, can also contain a metallisable group or asubstituent which can be converted into such a group, in the arylradical in o-position to the azo linkage such as, for example, again adisulphonylam-ido group or a carboxy, hydroxy or low alkoxy group. Inthis case, under suitable conditions, so-cal'led tricyclic complexes areobtained in which the formazane chain and the two substituents in theo-position thereto take part in the complex formation.

Vice versa, the aryl diazonium compound containing the sulphonylamidosubstituent in the o-position to the diazo linkage can also be used forthe production of an arylazomethylene or arylazomethine compound whichcan be coupled at the methylene or methine C atom respectively. It canbe coupled actually by methods known per so with an acylacetic acid oran ester or arylamide thereof, e.g. with a formyl phenylacetic acidalkyl ester or with an acetoacetic acid arylamide, or with a cyanoaceticacid .alkyl ester, and the coupling product can be saponified in analkaline medium to form an arylazomethylene or arylazomethine compoundwhich can be coupled. This is then coupled with a second aryl diazoniumcompound which can be identical with or different from the first to formthe formazane compound.

In addition, to produce the formazane compounds used according to theinvention, also the aryl diazonium compound containing thesulphonylamide group in o-position to the diazo linkage can first bereduced to the corresponding aryl hydrazine, this can be condensed withan aldehyde to form the hydrazone and the latter can be coupled with asecond aryl diazonium compound which can be identical with or differentfrom the first, to form the formazane compound. If the second diazocomponent does not contain a sulphonylamide group in o-position asdefined or if, in place thereof, it contains a metallisable group ofanother type, e.g. a hydroxyl or carboxyl group, then the order of thediazo components can be reversed. In both cases, the same asymmetricaldyestufis are obtained.

In the sulphonylamide group of the general Formula II, the sulphonylgroup bound to aliphatic radicals is ad vantageous or, even better, itis bound to aromatic radicals. Principally the sulphonylamide groups arederived either from low aliphatic sulphonic acids, preferably from themethyl, chloromethyl, ethyl and propyl sulpho-nic acids or fromsulphonic acids of the benzene series, mainly from benzene sulphonicacid, from homologous benzene sulphonic acids, from halogenated benzenesulphonic acids and also from those benzene sulphonic acids the benzenenuclei of which contain at least one water solubilising but not aciddissociating sulphonyl substituent such as, e.g., a methyl, chloromethylor ethyl sulphonyl group.

In the starting materials used according to the invention, the group ofthe general Formula II is advantageously a disulphonylamide group.Preferred starting materials are obtained, for example, by diacylatingthe amino group in o-nitroaminophenyl compounds. These can be reacted,for example, with 2 mols of alkyl or aryl sulphonic acid chloride orwith first one mol and then with another mol of two difierent sulphonicacid chlorides, advantageously in the presence of tertiary nitrogenbases such as, e.g. in a mixture of pyridine bases, and possibly in thepresence of an inert organic solubility promoter. The nitro group isthen reduced to the amino group, advantageously in a neutral medium withcatalytically activatedhydrogen or in a weakly acid medium according toBchamp. The o-aminodisulphonylamidophenyl compounds so obtained are usedas starting materials for the production of dyestufis according to theinvention in the form of their diazonium compounds or possibly afterconversion into the corresponding hydrazine compounds and condensationwith aldehydes to form hydrazone compounds.

The other starting materials necessary for the production of formazanecompounds of the general Formula I usable according to the invention arediazo components not contaim'ng metallisable groups, or o-hydroxyoro-carboxy-aryl diazonium compounds, also aldehydes in the form of thehydrazones mentioned above and, finally, methylene or methine compoundswmch can be coupled twice.

The components know in azo and formazane chemistry can be used as diazocomponents. In this case too, those of the benzene and naphthaleneseries are preferred. In stead of the o-hydroxyor o-carboxy-aryldiazonium compounds, possibly also the corresponding compounds can beused which contain in the o-position a substituent which can beconverted into such a metallisable group. In this case, the substituentis converted into the metallisable group in a suitable step.

Aromatic aldehydes are used principally for the produc tion of thehydrazone as they lead to particularly valuable mesoaryl formazanedyestuffs. For example, benzaldehyde, tolualdehyde, 3-nitrobenzaldehyde,2- or 4-chlorobenzaldehyde, 2,4-dichlorobenzaldehyde, benzaldehyde-Z,4-disulphonic acid, anisaldehyde, vanillin, 4-dimethylor4-diethylaminobenzaldehyde and 4-dihydroxyethylaminobenzaldehyde areused. Also heterocyclic aldehydes such as, e.g., furfural and pyridineor quinoline and benzimidazole aldehydes can be used and, finally,valuable end products are also obtained with aliphatic or araliphaticaldehydes such as, e.g. acetaldehyde, crotonaldehyde, caproaldehyde,phenacetaldehyde or cinnamaldehyde.

Also tit-carbonyl alkanes such as, e.g. acetone, acetophenone, as wellas chlorinated and/ or halogenated acetophenones, then nitroalkanes suchas nitromethane, also derivatives of malonic acid such as, e.g. theiresters and amides and, finally, also azolium salts containing activatedmethyl groups such as, e.g., the 2,3-dimethylbenzthiazolium or2,3-dimethylselenazolium or benzimidazolium salts can be used inaddition to the acyl and cyano acetic acid derivatives mentioned aboveas examples, asmethylene or methine compounds which can be coupled twiceat the methylene or methine C atom respectively, this possibly whilstsplitting ofi substituents.

The starting materials necessary for the production of the formazanecompounds'of the general Formula I can contain the substituents usual inazo dyestuffs, e.g., halogen, allryl, aralkyl, and aryl groups, alkoxyand aryloXy groups, cyano, nitro, sulphonic acid, sulphonic acid amide,sulphonic acid ester, carboxylic acid, carboXylic acid amide,alkylsulphonyl and arylsulphonyl groups, arylazo groups, then secondaryor tertiary amino groups and, fi-

. nally, also acylamino groups such as, eg, the acetylarnino andchloroacetylamino group.

The usual heavy metals of the atomic numbers 24 to 29 are used as agentsgiving off heavy metal for the metallisation of the metal-free formazanecompounds of the general Formula I. Chromium, cobalt, nickel salts andchiefly the copper salts of mineral acids or of low fatl,2,3-trimethyl-4 ty acids are used. It is also possible to use the complex salts ofthese metals, in which case it is possible for the groups bound incomplex linkage to the metal to appear in the end product. When mineralacid salts are used, the metallisation is performed advantageously inthe presence of an agent which buffers the mineral acid, as which areused in particular alkali hydroxides or carbonates or alkali metal saltsof low fatty acids such as, e.g. alkali acetates, or alkali metal saltsof polybasic oxygen acids of phosphorus, or ammonia or tertiary nitrogenbases such as, e.g., pyridine bases. The metallisation agent is used inat least equimolar amounts so that there is at least 1 heavy metal atomper mol dyestuff. Often the metallisation is completed even at roomtemperature, in many cases however, a light heating, e.g. to about isnecessary. In the process according to the invention, agents giving oilnickel and, chiefly copper are the preferred metallising agents as withthese, end products having particularly good dyeing properties areobtained;

A modification of the process according to the invention consists instarting from metallisable intermediate products of formazane compoundsof the general Formula I, first metallising these and only then formingthe finished dyestuff. Such intermediate products correspond, forexample, to the general Formula III wherein D represents an aryl radicalcorresponding to A or B,

Q represents a metallisable group in o-position to the azo linkage, and

R has the meaning given in Formula I.

These intermediates are obtained by coupling 1 mol of an aryl diazoniumcompound with a methylene or methine compound which, after completion ofthe coupling at the methine C atom, also contains a carboxyl group or asubstitutent which can be converted into such a group such as, e.g. acyano group or a carboxylic acid ester group. After such a substituenthas been converted into the carboxyl group if necessary, theintermediate product of the above formula is treated with the agentgiving oh heavy metal and then coupled with 1 mol of an aryl diazoniumcompound to form the metal-containing formazane dyestufi. Or" the aryldiazonium compounds used for the two couplings, as defined at least onemust contain as metallisable group a substituent of the general FormulaII in o-position to the diazo group. In this modified process, themetallisatio'n and the second coupling are performed in one single step.If the second coupling is performed in a sufiiciently alkaline medium,

then immediately beforehand also the cyano or carboXylic acid estergroup can be saponified in the same reaction medium.

metal correspond to the general formula wherein B represents a radicalof the benzene series,

Me represents a heavy metal selected from the group consisting of Cu andNi,

V represents a member selected from the group consisting of hydrogen,methyl and methoxy radicals,

X represents a member selected from the group consisting of loweraliphatic, phenyl, chlorophenyl, lower alkylphenyl, lower alkoxyphenyl,lower alkylsulphonylphenyl, sulphamylphenyl and N-loweralkylsulphamylphenyl radicals,

Y represents a metal binding group in o-position to the azo bondselected from the group consisting of -O and OOC-, and

Z represents a member selected from the group consisting of hydrogen,chlorine, methyl and sulphonic acid groups.

The phenyl nucleus B can be unsubstituted or substituted, for example,by chlorine or the nitro group. However, advantageously it contains agroup which increases the water solubility such as the sulphonic acidgroup or, in particular, a functionally converted sulphonic acid groupsuch as alkylsulphonyl, arysulphonyl and sulphonic acid amide groups,examples of which are the SO NH S0 NH-alkyl, -SO NH-aryl, SO N-dialkyland alkyl S O N aryl groups.

Particularly valuable dyestuffs are those in which Me is copper and Y is-O--.

The heavy metal-containing iormazane dyestuffs produced according to theinvention are worked up and isolated in the usual ways. Sometimes it isnecessary to finally cleanse them to remove undesired side products, forexample by dissolving and allowing to crystallise. Depending on theconstitution, red, brown, blue, violet, green to grey powders areobtained.

Dyestuifs according to the invention which do not contain watersolubilising groups are used as pigments and can be employed, forexample, for the dyeing of synthetic materials, lacquers, varnishes orspinning masses consisting of acetyl-celiulose or polyamides.

Those dyestufis which contain water solubilising groups such as, e.g.carboxylic acid or phosphonic acid and, mainly, sulphonic acid groups,are suitable for the dyeing and printing of leather, paper, and fibrousmaterial of the most different types, in particular of textile materialof natural or synthetic origin containing polypeptide groups such as,e.g. wool, silk, and nylon. For textile materials of this type, inparticular those dyestufis are used advantageously which contain asulphonic acid group, as many of them draw onto this material even froma weakly acid bath. Another valuable group are those dyestuffs accordingto the invention which, apart from groups possibly taking part in thecomplex formation, contain no acid dissociating groups, i.e. nocarbocyiic acid and sulphonic acid groups, but contain only substituentsfavouring the water solubility such as, e.g. low alkylsulphonyl groups,sulphonic acid amide groups and, at most, sulphonic acid amide groupssubstituted by low molecular hydrocarbon radicals. These dyestuffs havea very good aifinity to wool and material having similar dyeingbehaviour and they completely draw onto such materials from even aneutral to Weakly acid bath. If desired, the water solubility of suchdyestufis not containing sulphonic acid groups can be improved by theadmixture of anion active or non-ionogenic wetting or dispersing agentsor of reduc ng agents.

The textile dyeings produced with the dyestuffs according to theinvention are distinguished particularly by their good fastness to lightand rubbing and the excellent wet fastness properties such as, e.g., thegood fastness to washing, alkali, milling, sea water and decatising.addition, the dyeings are very pure and level.

Further details can be seen from the following examples. Where nototherwise expressely stated, parts are given therein as parts by weight.The temperatures are in degrees Centigrade. The relationship of parts byweight to parts by volume is as that of grammes to cubic centimetres.

EXAMPLE 1 26.4 parts of N-di-(methylsulphonyl)-amino-2-aminobenzene aredissolved in a mixture of 50 parts by volume of glacial acetic acid, 35parts or" concentrated hydrochloric acid and 50 parts of warm water andthe solution is quickly 'diazotised at 0-5 with 16.6 parts by volume of33.3% sodium nitrite solution. The diazoniurn solution is added dropwisewhile stirring well to a suspension of 204 parts of phenylformyl aceticacid ethyl ester in 200 parts or" water, 250 parts by volume of dioxanand 10.6 parts by volume of a 10 N-caustic soda lye, the addition beingmade at 0-10 and in the presence of such amounts of calcinated sodiumcarbonate that afterwards the reaction mixture has a weaklyphenolphthalein alkaline reaction. On completion of the coupling, thereaction is made weakly alkaline to brilliant yellow paper by theaddition of concentrated hydrochloric acid, the whole is diluted andbrought to the boil. After the addition of sufficient 1O N-caustic sodalye to ensure a strong alkaline reaction until the end of thesaponification, the reaction product is refluxed for 10 minutes. Thesolution of the saponification product is then made weakly alkaline tobrilliant yellow paper by the addition of concentrated hydrochloricacid, 31 parts of calciuated sodium carbonate are added and the whole iscoupled at 10-15 in the presence of 25 parts of crystallised coppersulphate (mol. weight 250) with the diazonium salt obtained bydiazotising 20.1 parts of Z-amino-l-hydroxybenzene-4- ethyl sulphone. Oncompletion of the coupling, the formazane copper complex compound issalted out at and filtered ofi. After drying, dark powder is obtainedwhich dyes wool, natural silk and polyamide fibres in intensive, pureblue shades.

If in the above example, the Z-amino-l-hydroxybenzene-4-ethyl sulphoneis replaced by 18.7 parts of 2- amino-l-hydroxybenzene-4-methyl sulphoneor by 24.9 parts of Z-amino-1-hydroxybenzene-4-phenyl sulphone, thendyestuffs having similar properties are obtained.

If, instead of using phenyl fonmyl acetic acid ethyl ester as couplingcomponent, 17.7 parts of acetoacetic acid phenylamide or 21.2 parts ofp-chloro-acetoacetic acid phenylamide are used and the saponification isperformed in the presence of sodium sulphite, then similar dyestuffs areobtained which dye wool in blue-violet shades.

EXAMPLE 2 CLN/CKN/OSOFOSO:NHZ

32.8 parts of Z-amino-l-hydroxybenzene-4-phenylsulphone-3'-sulphonicacid amide are dissolved in 100 parts of hot Water and 21 parts byvolume of 10 N-caustic soda lye, a solution of 6.9 parts of sodiumnitrite is added and, after cooling to the whole is stirred into amixture of 42 parts of concentrated hydrochloric acid, 100 parts ofwater and 30 parts of ice. Traces of excess nitrous acid are decomposedwith sulphamic acid. Sodium bicarbonate is then added until the reactionis neutral to Congo red paper and the brown-yellow suspension of thediazonium compound is poured at 0l0 into the suspension of 36.7 parts ofthe hydrazone (from 2-[N- di (methylsulphonyl) amino]-phenylhydrazineand benzaldehyde) M.P. l95-l96 in 200 parts by volume of pyridine and 25parts by volume of concentrated ammonia solution.

On completion of the coupling, 150 parts by volume of copper tetraminesulphate solution (corresponding to 6.4 parts of copper) are added tothe violet suspension of the dyestufif. After the addition of N-causticsoda lye until the reaction is alkaline to mimosa paper, the tricyclicblue formazane copper complex forms whilst a methylsulphonyl group issplit 01f. This complex is precipitated by the addition of sodiumchloride solution at 75 It is filtered ofi, Washed with dilute sodiumchloride solution and dried. After drying, it is a dark powder whichdyes wool, natural silk and polyamide fibres in fast blue shades.

If in the above example, the Z-amino-l-hydroxybenzene-4-phenylsulphone-3 sulphamide is replaced by 37.1 parts ofZ-amino-l-hydroxybenzene-4-sulphethyl anilide- 4-sulphamide or by 26.4parts of Z-amino-l-hydroxybenzene-4-sulphanilide, then dyestuifs havingsimilar properties are obtained.

EXAMPLE 3 32.9 parts ofZ-a-mino-l-hydroxybenzene-4-phenylsulphone-3-sulphonic acid aredissolved in 100 parts of hot water and 21 parts by volume of 10N-caustic soda lye, a solution of 6.9 parts of sodium nitrite is addedand, after cooling to 5, the whole is stirred into a mixture of 42 partsof concentrated hydrochloric acid and parts of ice water. The suspensionof the diazo compound is then made neutral to Congo red paper by theaddition of sodium bicarbonate and then coupled at 0-l0 as described inExample 2 with 49.1 parts of the hydrazone from 2-[N-di-(phenylsulphonyD-amino]phenyl hydrazine and benzaldehyde. Oncompletion of the coupling, parts by volume of copper tetramine sulphatesolution corresponding to 6.4 parts of copper) are added to the violetsuspension of the dyestuff. After the addition of 10 N- caustic soda lyeand stirring the reaction mixture for several hours, the tricyclic bluefor-mazane complex is formed whilst a phenylsulphonyl group is splitofi, which complex is precipitated, after quickly heating to 70-80, bythe addition of sodium chloride solution. It is filtered off, washedwith dilute sodium chloride solution and dried. After drying it is adark powder which dyes wool, natural silk and polyamide fibres inbeautiful blue shades Which have good fastness properties.

EXAMPLE 4 --so u 2C 3 l l f 54.4 parts ofN-di-(3-methylsulplronyl-phenylsulphonyl)-amino-2-arninobenzene areadded at (P10? while stirring well to 74 parts of 18.3% nitrosylsulphuric acid. The pale brown paste is then dissolved While stirring inice Water. The clear solution of the diazonium compound is then coupledas described in Example 1 with 20.4 parts of phenyl formyl acetoaceticacid ethyl ester. At the same time, sufiicien-t caustic soda lye isadded to ensure that after the addition of the diazoniurn component, thereaction mixture has a Weakly phenolphthalein alkaline reaction. Oncompletion of the coupling, the reaction is made weakly alkaline tobrilliant yellow paper by the addition of concentrated hydrochloricacid. The whole is diluted with water and boiled. Sufficient 10N-caustic soda lye is then added to the reaction mixture to ensure thatthere is a strong alkaline reaction until the end of the sapom'fication,and the reaction product is refluxed for 10 minutes. After the additionof 150 parts by volume of dioxan, the solution of the sap onificationproduct is again made Weakly alkaline to brilliant yellow paper withconcentrated hydrochloric acid, 31 parts of calcinated sodium carbonateare added and the whole is coupled at 10-15 in the presence of 25 partsof crystalline copper sulphate mol. Weight 250) with the diazoniurn saltobtained by diazotising 23.2 parts of5nitro-2-amino-1-hydroxybenzene-4-rnethylsulphone. On completion of thecoupling, the formazane copper complex is salted out at 80, filtered offand dried. It is a dark powder which dyes wool in fast greenish blueshades.

Dyestuffs having similar properties are obtained if in the aboveexample, the S-nitrQ-Z-amino-l-hydroxybenzenelmethylsulphone is replacedby 15.4 parts of 4-nitro-2- amino-l-hydroxybenzene or by 23.2 parts of6-nitro-2- amino-l-hydroxybenzene-4-methyl sulphone.

9 EXAMPLES soioni co SO2NHCH2CH2-CH3 Cu I E/ N N o 25.8 parts ofZ-aminobenzoic acid-S-sulphonic acid-npropylamide are indirectlydiazotised by the usual method and coupled with 20.4 parts ofphenylformyl acetic acid ethyl ester under the conditions described inExample 1. After the addition of sufficient caustic soda lye to ensure astrong alkaline reaction until the end of the saponification, thecoupling product is refluxed for 10 minutes. The solution of thesaponification product is made weakly alkaline to brilliant yellow paperby the addition of hydrochloric acid, 150 parts of crystallised coppersulphate solution (corresponding to 25 parts of crystallised coppersulphate) are added at l0 and the whole is coupled in the presence ofcalcinated sodium carbonate with the diazonium salt obtained accordingto Example 1 by diazotising 26.4 parts ofN-di-(methylsulphonyl)-amino-2-aminobenzene. The dicyclic formazanecopper complex is red coloured when it precipitates. It is filtered oiland washed with cold water. It is converted into the blue tricyclicformazane copper complex by treating with caustic soda lye in glycolmonomethyl ether whilst splitting oil a methylsulphonyl group. Thedyestufi is precipitated by the addition of sodium chloride solution,filtered off and washed. After drying, it is a dark powder which dyeswool in very fast, pure blue shades.

EXAMPLE 6 26.4 parts of N-di-(methylsulphonyl)-arnino-2-arninobenzeneare diazotised as described in Example 1, coupled with 20.4 parts ofphenyl =for'myl acetic acid ethyl ester and saponified with caustic sodalye. The alkaline solution of the saponification product is coupled withthe diazonium' salt obtained by diazotising 38.8 parts of N-di-(phenylsulphonyl)-amino-2-aminobenzene, sufiicient sodium carbonatebeing added to ensure an alkaline reaction until the coupling iscomplete. The precipitated brownred dyestuil is filtered oil and washedwith cold water. By dissolving the dyestuff in 300 parts by volume ofglycol monomethyl ether and adding caustic soda lye, a phenylsulphonylgroup is split olf. The violet solution of the formazane dyestutl ismade weakly alkaline to litmus paper by the addition of acetic acid, 150parts by volume of copper sulphate solution (corresponding to 6.4 partsof copper) are added and the whole is heated at 8090 until the bluecopper complex compound has formed. The dyestuff is precipitated by theaddition of sodium chloride solution, filtered off, washed with dilutesodium chloride solution and dried. It dyes polyamide fibres in fast,blue shades.

EXAMPLE 7 l II 38.8 parts ofN-di-(phenylsulphonyl)-arnino-2-aminobenzene in 250 parts by volume ofglycol monomethyl ether, 35 parts of concentrated hydrochloric acid and20 parts of water are directly .di-azotised at 0-5 with 16.6 parts byvolume of 33.3 sodium nitrite solution, the diazoniurn salt is coupledwith 20.4 parts of phenyl formyl acetic acid ethyl ester and thecoupling product is saponified 'with caustic soda lye. The solution ofthe saponification product is made alkaline to brilliant yellow paper bythe addition of concentrated hydrochloric acid and at 10-15 150 parts byvolume of diox-an and 150 parts by volume of a nickel sulphate solution(corresponding to 5.9 parts of nickel) are added. The whole is coupledin the presence of 31 parts of calcinated sodium carbonate with thediazonium salt obtained by diazotising 18.9 parts ofZ-amino-1-hydroxybenzene-4-sulphonic acid. On completion of thereaction, the tormazane nickel complex compound is salted out at 70,filtered off and washed with sodium chloride solution. After drying, adark powder is obtained which dyes wool from a weakly acid bath in fastviolet shades.

EXAMPLE 8 SOaH 38.8 parts of N di-(phenylsulphonyl) amino-2-aminobenzeneare diazotised as described in Example 7 and coupled with 20.4 parts ofphenyl for-myl acetic acid ethyl ester. On completion of the coupling,the reaction mixture is made alkaline to brilliant yellow paper by theaddition of concentrated hydrochloric acid, then diluted and boiled.After the addition of sufficient l0 N-caustic soda 'lye to ensure astrong alkaline reaction until the end of the saponification, thereaction product is refluxed for 15 minutes. The solution of thesaponification product isthen made alkaline to brilliant yellow paperagain by the addition of concentrated hydrochloric acid, parts by volumeof dioxan are added and, at l0l5, parts by volume of a nickel sulphatesolution (corresponding to 5.9 parts of nickel) are added. The whole iscoupled in the presence of 31 parts of calcinated sodium carbonate with25 parts of the diazonium oxide ofl-amino-Z-hydroxynaphthalene-4-sulphonic' acid. On completion of Iii.-the coupling and complex formation, the formaz-ane nickel complexcompound is salted out at 605, filtered off and Washed with dilutesodium chloride solution. After drying, a dark powder is obtained whichdyes Wool in fast beautiful reddish blue shades.

EXAMPLE 9 54.4 parts of N(ii-(3-methylsulphonylphenylsulphonyl)amino-Z-arnincbenzene arediazotised as described in Example 4 and coupled with 20.4- parts ofphenyl formyl acetic acid ethyl ester. On completion of the coupling,the reaction mixture is made alkaline to brilliant yellow paper by theaddition of concentrated hydrochloric acid, diluted and boiled. Afterthe addition of sufficient N-caustic soda lye to ensure a strongalkaline reaction until the end of the saponific-ation, the reactionproduct is refluxed for 10 minutes. After the addition of 150 parts byvolume of dioxan, the solution of the saponification product is thenmade alkaline to brilliant yellow paper by the addition of hydrochloricacid at 1015 and at this temperature, 159 parts of a copper sulphatesolution (corresponding to 6.4 parts of copper) are added. The olivegreen suspension is coupled in the presence of 31 parts of calcinatedsodiumcarbonate with the diazomum salt obtained by diazotising 32.8parts of amino-1-hydroxybenzene-4-phenylsulphone 3' sulphonic acidamide. On completion of the reaction, the formaza-ne copper complexcompound is salted out at 80, filtered off, washed with dilute sodiumchloride solution and dried. After drying, a dark powder is obtainedwhich dyes wool from a neutral bath in very fast pure blue shades.

If in the above example the Z-amino-l-hydroxybenzene-4-phenylsulphone-3-sulphonic acid amide is replaced by 18.7 parts ofZ-amino-1-hydroxybenzene-4-methylsulphone or by 20.1 parts ofZ-arnino-l-hydroxybenzenel-ethylsulphone, then dyestufis having similarproperties are obtained.

The dyestuffs given in the following table are also produced by theprocesses described in the Examples 1 to 9.

Formazane compound Metal Shade on woolN-(2-hydroxy-S-n-propylsulphonylphenyl)- N(2'-ethylsulphonylaminophenyl) -msphenyl-formazane.

N-(2-hydroxy-fi-phenylsulphonylphenyD- N-(2-methylsu1phonylaminophenyl)-msphenyi-formazane.

N-(2hydroxy-5-phenylsulphonylphenyl)- N(2-ethylsulp'nonylaminophenyl)-msphenyl-lormazane.

N -[2-l1ydr0xy 5- (m-sulphonic acl d amide) phenyl-Sulph0nylphenyl]-N-(T-ethylsulphonylaminopheuyl) unephenyl-formazane.

N-[Z-hydroxyfi-(m-sulphorric acid methylarnide)-phenylsulphonylpheny1]-N- (2- ethylsulphonylaminophenyl)-ms-phenylformazane.

N-[Z-hydroxy-S-(m-sulphonic ac1d)-phenylsulphonylphenyl]-N-(2-ethylsulphonylaminophenyl)-ms-phcnyl-lormozanc.

N-[Z-hydroxy-S-(m-sulphonlc acid)phenylsulplionylphenyl]-N-(2-p-chlorophenylsulphonylmnlnophenyl)ms-phenylformazane.

N -[2-hydroxy-5 (m-sulplionicacid)-phenylsulphonylphenyll-N-(2-p-rnethylpheuylsulphonylaminophenyl)-ms-phenyliotmazaue.

N -[2-hydroxy-5-(sulphonic acidphenylamide)-pheuyl]-N-(2-ethylsulphonylaminopheuyl)-ms-phenyl-iorinazane.

N-[2-l1ydr0Xy-5-(sulphouic acid phenylamide) phenyl] -N(2-n-propysulpl1onyl aminophenyl)-ms-phenyl-formazane.

N -[2-hydroxy-5(sulphonic acidphenylamide)'phenyl]-N-(2pheny1su1phonylaminophenyl)-ms-phenyl-formazane.

N-[2-hydroxy-5-(sulphonicacid-p-hydroxyphenylamide)-phenyl]-N-(2-rnethylsu.lphonylaminophenyl)-ms-phenyl-formazaue.

N-[2-hydroKy-5-(su1phouieacid-p-hydroxyphenylamide)-phenyl]-N-(2-phenylsulphonylaminophenyl)-ms-pheny1-iormazane.

N-[2-hydroxy-5-(sulphonic acidphenylamidc)-phenyl]-N-(2-rnmethylsulphonylphenylsulphonylaminophenyl)-ms-phenyl-forrnazanc.

N-[2-hydroxy-5-(sulphonic acid phenylamide)-phenyl]-N-(2-pchlorophenylsulphonylaminophenyl)-rns-phenyl-iorma- Zane.

N-(2-11ydr0xy-S-methylsulphouylphenyl)-N-(2'-phenyl-sulphonylaminopheuyl)- ms-phenyl-formazane.

N-(2-hydrow-S-ethylsulphonylphenyl)- N (2-phenylsulphonylaminophenyl)-ms-phenyl-formazaue.

N-(Z-hydr0xy-3-nitro-5-mcthylsu1pbonylphenyl)-N-(2-phenylsulphonylaminophenyl)-ms-phenyl-formazane.

N-(2-hydroxy-5-nitrophenyl)-N-(2-pheny1-sulphonyl-amiuophenyl)-ms-phcnylformazane.

N-(2-hydroxy-4-nitro-5-methy1sulphonylphenyl) -N-(2-phenylsulphonylaminophenyl)-ms-pheuy1-fonnazane.

N-[ 2-carb0xy-4 (SulphOnic acid methylarnide) -pheny1]-N-(2-pl1enylsulphonylaminophenyl)-ms-phenyl-f0rmazane.

N-[2-earboxy-4-(su1phonie acid phenylamide) -phenyl]-N-(2-pheny1sulphonylaminophenyl)-ms-phenyl-iormazane.

N-[2-carboxy-4-(sulpl1onic acid-N-methylphcnylamide) -phenyl]-N(2-phenylsulphonylaminophenyl) ms phenyl forma zane.

N-[ 2-carboxy-4- (sulplionic acid amide) pheny1]- N -(2-phenylsnlphonylamino phenyl)-ms-pheuyl-tormazane.

N-(2-carboxy-4-sulphonic acidamidephenyl)-N-(2-methylsulphonylaminophenyl)-rus-pheuyl-formazane.

N-(2-carboxy-4-sulphonic acid amidephenyl) -N- (2-n propylsulphonylaminopheuyl)-ms-phenyl-formazane.

N-[2-carboxy-4- (sulphonic acid-N-mcthylphenylamide)-nhenyl]-N (2-rnethyls ulph onylaminophenyl) ms phenyl Korma zane.

N-(2-carboxy-4-sulphonic acid amide phenyl) -N(5-methyl-2-methylsulphonylamiuophenyl)-ms-phenyl-forrnazane.

N-(2-earboxy-l sulphonic acid amidephcnyl)-N-(5-methoxy-2-methylsulphonylaminophenyl)-ms-phenyl-forrnazaue.

N -[2-hydrcxy-5-(m-sulphonic acid amide)- phenylsulphonylphenyl] N (2phenylsulphonylaminophenyl)-ms-phenyl-iorm- Ni Cu Ni Cu Ni Cu Ni Cublue.

violet.

blue.

violet. blue.

violet. blue.

violet. blue.

violet. blue.

greenish blue.

blue.

greenish blue.

blue.

brown.

blue.

'13 TABLE Conti.uued

For'mazane compound Metal wool Shade on N-(2-hydroxy-3-nitro-5-methylsulphony1- phenyl) -N (2'-methylsulphonylaminplienyU-ms-phenyl-iormazaue.

N (Q-hydroxy--nitro--methylsu1phonylphenyl) -N (2-methy1sn1phonylaminophenyl)-msphenyl-fom1azane.

N- (2-11ydroxy-5-nitrophenyl-3-sulph onic acid) N(2-phenylsulphcnylaminophenyl) -ms-phenyl-formazaue.

N-l2-hydr0sy-5-(m-sulph onic acid amide) plienyl-phenyfl-N -(2l-phenylsu lp-honylaminophenyl) -ms-bhenyl-form azane.

N-[Z-hydrow--sulphc-nic acid naphthyl- (a) ]-N' (2-phenylsulphonylaminophenyl) -msphenyl-iorm azane.

noihenyl} -ms-phenyl-ormazane.

greenish blue.

blue.

46 blueish green.

47- olive green.

violetty grey. blue.

N-(2-hydroxyoethylsulphonylphenyl)- I- (2 -p-chl0rophenylsulphonylaminophenyl.)-ms-pheny1-formazaue.

N-[2-hydroxy-(m-sulphonic acid amide)- phenylsulphonylphenyH-N--p-chloroph enylsulphonylaminophenyl) -msphenyl-iormazane.

N [Z-llydIOhY-5(5111131301110 acid-N-ethyl-N-4-sulphcphenylamide)-phenyl]-N'-(2'- p11enylsulphonylaminophenyl)-Ins'phenyl-lormazme.

N-{Q-hydroxy-S-(sulphonic acid-p-hydroxypheny1amide)-phenyl]-N-m-methylsulphonylphenylsulphonylaminophenyl)- ms-phenyl-formazane.

N'l2-hydroxy-fi-(sulphonic acid methylamid o) -phenyl]-N-(2-m-methyl5ulphonylpheuysulphonylaminophenyl)- ms-phenyl-iormazane.

N-(2-hydro:;yphenyl) -N-[2"(m-sulphonic acidamide-phenylsulphonylamiuo)- phenyll-msqo-chlorophcnyl-iormazane.

N -(2-1:ydroxy-S-chlcrophenyl) -N -[2 (msulphonic acid diethylamidephenylsulpli onylarnino) -pheuyl]-ms-o-sulphcnic acid phenyl-iormazane.

5L.-- Cu Ni Cu violet. blue.

Ni Cu violet. 7 blue.

methylamide-phenylsulphonylamino)- pl enyl]-ms-p-methylphenyl-formaZane.

N-[2-hydrOXy-5-(sulph onic acid-NethyLN- 4-Sulphophenylarnide)phenyl]-N-(2-p-erhylphenylsulphonyl-aminophdenyD-ms-phenyl-io Ni Cu violet. blue.

violet. blue.

EXAMPLE 4 parts of the coppercontaining dyestuif obtained according toExample 9 are dissolved in 4000 parts of water and 1&0 parts of wellwetted wool are introduced into the dyebath at 4050. The bath is broughtto the boil within half an hour, kept boiling for 45 minutes and thenthe wool is rinsed with cold water and dried. A biue dyeing is obtainedwhich has very good fastness to wet, alkali, rubbing and light.

What we claim is:

1. Dyestuffs of the formula wherein B is a member selected from thegroup consisting of unsubstituted phenyl, sulfophenyl, nitrophenyl,chlorophenyl, lower alkylsulfonylphenyl, phenylsulfonylphenyl,sulfamyl-phenylsulfonylphenyl, sulfophenylsulfonylphenyl, Nmethylsulfamyl phenylsulfonylphenyl, sulfamylphenylphenyl,chloromethyl-sulfonylphenyl, sulfamyiphenyl, N-rnono and di-loweralkylsulfamylphenyl, N-phenylsulfamylphenyl, N-parahydroxyphenylsulfamylphenyl, N-phenyl-N-lower alkylsulfamylphenyl,N-sulfophenyl-N-lower alkylsulfamylphenyl, and N-sulfamyl-phenyl -N-lower alkyl-sulfamylphenyl,

Me is a heavy metal selected from the group consisting of Cu and Ni,

V is a member selected from the group consisting of hydrogen, methyl andmethoxy,

X is a member selected from the group consisting of lower aliphatic,phenyl, chlorophenyl, lower alkyl phenyl, lower alkoxyphenyl, loweralkylsulphonylphenyl, sulphamylphenyl and N-lower alkylsulphamylphenyl,

Y is a metal binding group in o-position to the azo bond selected fromthe group consisting of O and -OOC--, and

Z is a member selected from the group consisting of hydrogen, chlorine,methyl and sulphonic acid.

2. The formazane dyestuif of the formula i N N 15 16 3. The formazanedyestuff of the formula 5. The formazane dyestufi of the formula O-smomI s o 20 6. The formazane dyestuff of the formula 4. The formazanedyestufi of the formula Osm-Osomm UNITED STATES PATENTS 2,182,055Schweitzer Dec. 5, 1939 2,662,074 Brooks Dec. 8, 1953 45 2,756,223Schetty July 24, 1956 2,864,815 Zlegler Dec 16, 1958 3,030,353 KusterApr. 17, 1962

1. DYESTUFFS OF THE FORMULA